Azo dyestuffs containing chromium and process of preparing them



Patented Nov. 10, 1936 UNITED STATES 2,060,563 PATENT OFFICE AZO DYESTUFFS CONTAINING CHROMIUM AND PROCESS OF PREPARING THEM Erich Fischer, Bad Soden-on-the-Taunus, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application September 22, 1934, Serial No. 745,166. In Germany September 27,

10 Claims.

wherein R stands for an aryl radical, R1 stands for an aryl radical or the group COOalkyl, R2 stands for an aryl radical containing a carboxylic acid group in one ortho-position to the azo-group and no hydroxy group in the other ortho-position to the azo-group and wherein, furthermore, at least one of the radicals R and R2 must contain at least one sulfonic acid group.

The resultant azo-dyestuffs containing chromium have a better fastness to fulling than the dyestuffs analogous thereto which have in 3-position of the pyrazolone nucleus a carboxylic acid or alkyl group.

The above mentioned pyrazolone-azo-dyestufis are obtainable by coupling diazotized orthoamino-aryl-carboxylic acids which contain no hydroxy group in ortho-position to the amino group with 3-phenyl-5 pyrazolones -or -pyrazolone-3-carboxylic acid alkyl esters, the components being chosen so that the dyestuffs contain at least one sulfonic acid group.

As diazo components which come into consideration for the preparation of, the starting materials used in the present process the following may, for instance, be mentioned: Z-aminobenzene-l-carboxylic acid, S-bromo-Z-aminobenzene-l-carboxylic acid, 3,5-dichloro-2aminobenzene-l-carboxylic acid, 5-chloro 2 aminobenzene-l-carboxylic acid, 4-aminodiphenyl-3-carboxylic acid, 4-nitro-2-aminobenzene-1-carboxylic acid, 4-sulfo-2-aminobenzene-l-carboxylic acid, 5sulfo-2-aminobenzene-l-carboxylic acid, 3,5-disulfo-2-aminobenzene-l-carboxylic acid, 3- chloro 5 sulfo 2 aminobenzene-l-carboxylic acid, 2,3-aminonaphthoic acid or the like.

For the preparation of the starting dyestuffs there may be used as coupling components, for instance, the following pyrazolone compounds: 1-phenyl3-phenyl-5-pyrazolone, 1-phenyl-5-pyrazolone-iS-carboxylic acid ethyl ester, 1-(2'- chlorophenyl) 3 phenyl 5 pyrazolone, 1-(2- chloro- 5sulfophenyl) 3 phenyl-5-pyrazolone, l-(3-sulfopl1eny1) 3 phenyl 5 pyrazolone, 1- (2 -sulfophenyl) -3-phenyl-5-pyrazolone, 1- (4- methyl- 2 sulfophenyl) -3-phenyl-5-pyrazolone, 1- (4'-chloro-2sulfophenyl) -3-phenyl-5-pyrazo-4 lone, l-(2,4-dimethyl6-sulfophenyl) 3 phenyl-5pyrazolone, 1- (2-sulfophenyl) -5-pyrazolone-3-carboxylic acid ethyl ester, 1-(4-chloro- 2-sulfophenyl)5pyrazolone-3-carboxylic acid methyl ester, 1-(4-methyl-2-sulfophenyl)-5- pyrazolone-3-carboxylic acid butyl ester, 1-(2- methyl-6-chloro-4-sulfophenyl) 3-phenyl-5-pyrazolone, 1- (2'-sulfophenyl) --3- (4 '-carboxyphenyl) -5-pyrazolone, 1- (2'chloro-5'-sulfophenyl) 3- (4-methylphenyl) -5-pyrazolone, 1- (4'-sulfo phenyl) -5-pyrazolone 3 carboxylic acid ethyl ester, 1- (2',5'-disulfophenyl) -3-phenyl-5-pyrazolone, 1-(2',4'-disulfophenyl) 5 pyrazolone-3- carboxylic acid ethyl ester, 1-(2'-carboxy-5'-sulfopheny1)3-phenyl 5 pyrazolone, 1-(4-su1fonaphthyl) -3-phenyl-5-pyrazolone,

1-(2'- hydroxy 3'- carboxy 5- sulfophenyl) -3- phenyl- 5 -pyrazolone, 1-(2',4'-dichloro-6'-sulfopheny) -3-phenyl-5-pyrazolone or the like.

The treatment of the dyestuifs with the agents yielding chromium may be effected in known manner by heating in open vessels, under reflux or under raised pressure. As agents yielding chromium there may be used, for instance chromium chloride, chromium fluoride, chromium formate or chromium acetate or other organic or inorganic chromium salts.

The products made in accordance with the invention are suitable, for example, for dyeing animal fibers like wool, natural and loaded silk and leather.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight:

(1) 544 parts of the azo-dyestuif obtainable from diazotized ortho-amino benzoic acid and 1-(2,5'- disulfophenyl) 3 phenyl- 5-pyrazolone are dissolved in 5000 parts of Water and heated to boiling under reflux with 300 parts of chromium formate (corresponding to 92 parts of chromium oxide) until the formation of the chromium complex is finished. The excess of chromium salt is removed by means of sodium carbonate and the filtered and neutralized solution is concentrated by evaporation. The powder obtained which is easily soluble in water yields according to the dyeing methods usually applied with dyestuffs containing chromium reddish-yellow even dyeings of very good fastness properties.

(2) 464 parts of the dyestufi obtainable from diazotized ortho-aminobenzoic acid and 1-(2'- sulfophenyl)-3-phenyl-5-pyrazolone are heated to boiling, under reflux, for about 30 hours in an aqueous solution with chromium fluoride corresponding to 92 parts of chromium oxide. The dyestuff containing chromium is salted out by means of sodium chloride. It yields reddishyellow very even dyeings of very good fastness to light and good fastness to washing.

(3) By replacing in the Examples 1 and 2 the dyestuffs used therein by 661.5 parts of the pyrazolone-azo-dyestuff of the following formula:

CODE 8. dyestuff of similar properties is obtained which yields shades of a more greenish hue.

(4) 540 parts of the dyestuff obtainable from diazotized ortho-aminobenzoic acid and 1-(2,ldisulfophenyl) -5-pyrazolone 3 carboxylic acid ethyl ester are heated to boiling in an aqueous solution with chromium formate. The chromium compound of the dyestuif thus obtained yields on wool yellow dyeings of good fastness properties.

(5) The chromium compound of the dyestuff of the following formula:

I COOH which is obtainable by boiling for several hours a solution of 714.5 parts of the dyestufi in water with a chromium formate solution corresponding to 92 parts of chromium oxide is distinguished by greenish-yellow dyeings of good fastness properties.

(6) 544 parts of the dyestufi obtainable from diazotized 5-sulfo-2-amino-1-benzoic acid and 1 (4'-sulfophenyl) -3-phenyl 5 pyrazolone are heated to boiling in a 10 per cent aqueous solution with chromium fluoride until the formation of the chromium complex is finished. The dyestufi containing chromium dyes wool reddishyellow tints of good properties.

('7) By replacing in the preceding examples the dyestuffs mentioned therein by 589 parts of the dyestuff of the following formula:

SOsH

Hogs

a dyestuif of similar properties is obtained which yields reddish-yellow tints.

(8) 464 parts of the dyestuff obtainable from diazotized ortho-aminobenzoic acid and 1- (2 ,4 -dimethyl-6 -sulfophenyl) -3- phenyl -5 pyrazolone are heated at C. for 4 hours in an autoclave, while stirring, in an aqueous solution with chromium formate corresponding to 92 parts of chromium oxide. The chromium compound of the azo-dyestufi is completely salted out and, in the dry state, forms a yellow powder. It dyes wool yellow tints of excellent fastness to light, very good evenness and good fastness to washing.

I claim:

1. The process of preparing azo-dyestuffs containing chromium which comprises heating pyrazolone-azo-dyestuifs of the general formula:

wherein R stands for a radical of the benzene or naphthalene series, R1 for the group -COO-a1- kyl or for a radical of the benzene series, R2 represents a radical of the benzene, naphthalene or diphenyl series containing a carboxylic acid group in one o-position to the azo-group and no hydroxy group in the other o-position to the amgroup and wherein at least one of the radicals R and R2 contains at least one sulfonic acid group, with agents yielding chromium.

2. The process of preparing azo-dyestufis containing chromium which comprises heating pyrazolone-azo-dyestufis of the general formula:

X; SOIH wherein R1 stands for the group COOalkyl or for a radical of the benzene series, R2 represents a radical of the benzene series containing a carboxylic acid group in one o-position to the azogroup and no hydroxy group in the other oposition to the azo-group, and X1 stands for a member of the group consisting of hydrogen, methyl and chlorine and X2 for a member of the group consisting of hydrogen, methyl, chlorine and the sulfonic acid group, with agents yielding chromium.

3. The process of preparing an azo-dyestuff containing chromium which comprises heating a pyrazolone-azo-dyestufi of the formula:

SOzH

with an agent yielding chromium.

VII

4. The process of preparing an azo-dyestuff containing chromium which comprises heating a pyrazolone-azo-dyestuif of the formula:

with an agent yielding chromium.

5. The process of preparing an azo-dyestuff containing chromium which comprises heating a pyrazolone-azo-dyestufi of the formula:

with an agent yielding chromium.

6. The chromium compounds of the azo-dyestuffs of the general formula:

wherein R stands for a radical of the benzene or naphthalene series, R1 for the group COO alkyl or for a radical of the benzene series, R2 represents a radical of the benzene, naphthalene or diphenyl series containing a carboxylic acid group in one o-position to the azo-group and no hydroxy group in the other o-position to the azo-group, wherein at least one of the radicals R and R2 contains at least one sulfonic acid group, and wherein the carboxylic acid group of the radical R2 standing in o-position to the azobridge, in combination with this azo-bridge, contains bound chromium, which products form yellow to orange powders which dye the animal fiber yellow to orange tints of good fastness properties.

7. The chromium compounds of the azo-dyestuffs of the general formula:

sents a radical of the benzene series containing a carboxylic acid group in one o-position to the azo-group and no hydroxy group in the other o-position to the azo-group, X1 stands for a member of the group consisting of hydrogen, methyl and chlorine, X2 for a member of the group consisting of hydrogen, methyl, chlorine and the sulfonic acid group, and wherein the carboxylic acid group of the radical R2 standing in o-positicn to the azo-bridge, in combination with this azo-bridge, contains bound chromium, which products form yellow to orange powders which dye the animal fiber yellow to orange tints of good fastness properties.

8. The chromium compound of the azo-dyestuff of the formula:

wherein the carboxylic acid group, in combination with the azo-bridge, contains bound chromium, which product forms a yellow powder dyeing the animal fiber reddish-yellow tints of very good evenness, very good fastness to light and good fastness to washing.

9. The chromium compound of the azo-dyestufi of the formula:

wherein the carboxylic acid group, in combination with the azo-bridge, contains bound chromium, which product forms a yellow powder dyeing the animal fiber yellow tints of very good evenness, very good fastness to light and good fastness to washing.

10. The chromium compound of the azo-dyestuff of the formula:

wherein the carboxylic acid group, in combination with the azo-bridge, contains bound chromium, which product forms a yellow powder dyeing the animal fiber yellow tints of very good evenness, very good fastness to light and good fastness to washing.

ERICH FISCHER. 

